Enhanced polarization fatigue behavior in lead-free ferroelectric (K, Na)NbO₃ thin films by Mn doping

Potassium sodium niobate (KNN) has attracted much interest as a promising lead-free ferroelectric candidate with its excellent physical properties for potential applications to novel nano-devices such as non-volatile ferroelectric memory. However, the use of KNN films in actual devices has been limited due to concerns in operational reliability (i.e., a polarization fatigue property). In this work, we demonstrate the enhancement of a polarization fatigue behavior in KNN thin films by doping of Mn ions. Ferroelectric fatigue is significantly suppressed in 0.4 mol% Mn-doped KNN films compared with pure KNN films. The amounts of mobile charged defects (e.g., oxygen vacancies and hole carriers produced with cation vacancies) are reduced in the presence of multivalent Mn dopants resulting in a decrease of leakage current density. The reduction of charged defect density can weaken the domain wall pinning effect enabling the polarization fatigue to be suppressed in KNN films. Our work is of practical interest for realizing lead-free ferroelectric memory devices with high performance.